Permanent waving compositions comprising 2, 2, 2-trichloro-1, 1-ethanediol



United States Patent 3,109,77 8 PERMANENT WAVIN G COMPOSITIONS COMPRIS- IYG 2,2,2-TRlCHLORO-1,l-ETHANEDIOL Albert Shansky, Bettswood, Norwalk, and Arthur Tarasov,

Trumbull, Conn., assignors to Turner Hall Corporation,

New York, N.Y., a corporation of New York No Drawing. Filed Mar. 16, 1961, Ser. No. 96,084

6 Claims. (Cl. l6787.1)

This invention relates to new methods and compositions for placing hair on the human head in temporarily and permanently waved configuration. In one specific aspect, the invention pertains to permanent waving by first softening the hair to break down certain chemical linkages of the hair keratin, and, subsequently, with the hair 1n waved configuration, hardening the hair again in its new configuration by use of new and improved compositions and process for hardening the hair. In another specific aspect, the invention pertains to the provision of a new process and composition for placing the hair in temporarily waved configuration, this treatment conventionally being known as setting.

Referring first to permanent waving of hair on the hu man head, conventionally, the hair is first softened by application of a waving solution which includes a chemical reducing agent. The reducing agent employed almost universally in cold waving solutions for human hair is the mercaptan thioglycollic acid which is used in the form of its ammonium salt, namely, ammonium th-ioglycollate. Other mercaptans can be used, however, as can certain members of the class of compounds known as sulfites. For examples of other mercaptans usable for softening hair and concentrations and pHs at which they are used, see McDonough Patent No. 2,577,710, dated December 4, 1951. It is generally accepted theory in the hair waving field that the reducing agent softens the hair by breaking the disulfide bonds of the hair keratin which is the basic constituent of the hair. The specific linkage which is broken is the cystine linkage, and the breakage of each linkage produces two sulfhydryl groups. The softened hair is placed in waved configuration and then rehardened so that it is returned to its original resilient condition and so that it will retain the wave. The hardening step conventionally involves rebuilding a good portion of the broken disulfide bonds, and ordinarily solutions of hydrogen peroxide or alkaline perborates or bromates are employed for this purpose.

One of the drawbacks associated with conventional methods of permanent waving as briefly outlined above is that the hair has a tendency to appear curly when Wet but straighter when dry. We have found that this is due to the fact that upon drying (after rehardening) the rebuilt cystine linkages relax for reasons to be discussed hereinafter. This difficulty is of great significance since it results in permanent waves wherein the hair ultimately does not have the desired shape which had been imparted to it when wet, so that not only is the patron disappointed .in the ultimate result, but the beauty operator has ditficulty in gauging just what the final result will be when the hair is dry.

Adverting now to setting, i.e., imparting a transient or temporary alteration to the shape of hair which is not to be permanently waved, conventionally, this has been done in several ways. For example, one common method involves use of gums and other film forming chemicals such as lacquers and Water soluble plastic solutions in liquid form or as aerosol sprays. These materials form a surface film on the hair and tend to hold it in shape by stiffening it. Possibly the most common method is simply to use water which gives the least desirable results but avoids some of the drawbacks .of other methods such as stickiness, guminess, flakiness, dullness, malodorousness, and other undesirable results of placing on the hair the various chemicals involved.

Generally, present methods and compositions for im' parting a temporary setting to hair on the human head are not very satisfactory since they lack permanence with respect to dampness and the usual physical displacement caused by wind, tousling, sleeping and so on. Also, as already mentioned, unsightly and undesirable efiiects are sometimes produced as a result of using the various chemicals conventionally employed for setting.

It is a principal object of the present invention to pro- Wide a method and compositions for hardening hair that has been softened for the purpose of cold permanent waving, whereby the wave imparted not only does not relax when the hair dries but, on the contrary, tightens somewhat.

It is another object of the present invention to provide a method and compositions of the character described wherein the degree of tightening of wave formation after drying of the hair can be controlled.

It is an additional object of the present invention to provide a method and compositions of the character described wherein the wave imparted is longer lasting.

It is a further object of the present invention to provide a method and compositions of the character described which are simple and inexpensive to practice and which have all of the advantages of conventional hardening methods and compositions but none of the disadvantages thereof.

It is another principal object of the present invention to provide a method and composition for imparting a temporary set to hair on the human head which is longerlasting, more resistant, and more desirable than the set' obtainable by conventional hair setting methods and compositions.

It is another object of the present invention to provide a setting method and composition of the character described wherein stickiness, flaking and other undesirable characteristics of present day methods and compositions are obviated.

It is a further object of the present invention to provide a setting method and composition of the character described which make use of a chemical reaction with a constituent of the hair in order to obtain the desired results.

Other objects of the invention in part will be obvious and in part will be pointed out hereinafter.

The invention, accordingly, consists of the series of steps and compositions of matter hereinafter described and of which the scope of application will be indicated in the appended claims.

Referring first to the permanent waving aspect of the present invention, the cystine linkage in hair keratin as it occurs naturally is considered to be a true covalent bond. We believe that when reduced hair, i.e. hair in which the cystine linkages have been broken, is rebonded by the conventional oxidation means, the true covalent bonds are not restored and that the new bonds produced are influenced by Van der Waals forces. Such bonds are quite weak and can be rebroken by mere mechanical action. In addition, in the case of bonds produced by Van der Waals forces, the distance between atoms is not markedly different whether the substance is Wet or dry; as a result, when the hair loses moisture, it tends to relax because the loss of water which aids in supporting the bonds is not compensated for by a decrease in atomic distances of the rebonded sulfur atoms during exsi-ccation.

Pursuant to the aspect of the present invention now under discussion, a new system of rejoining the broken cystine linkages is provided wherein true covalent bonds are formed. In the case of such bonds, the true atomic distances are assumed as the substance dries (these being lesser distances than when the substance is wet), and this tends to prevent relaxation of the bonds during exsiccation and actually has the tendency to tighten them. As a result, hair which has been softened and placed in a waved configuration, and which is then rehardened while in saidconfigu-rat-ion pursuant to the present invention, will tend to tighten, i.e. curl slightly, on drying, and at the least relaxation will certainly be reduced.

In accordance with the present aspect of the invention, we have found that the broken disulfide linkages of softened hair can be joined into new bonds at the cyst-ine site by employing water soluble polyha logenated open chain compound having at least two halogen atoms on a single carbon atom and including at least one water solubilizing group selected from the class consisting of hydroxyl groups, carbonyl groups and sulfonate groups.

The process of joining sulfur atoms to build new bonds at the cystine site pursuant to the present invention will be referred to hereinafter as alkylation, regardless of whether sulfhydryl groups produced by chemical reduction (as in the instant aspect of the invention) or naturally occurring free sulhyd-ryl -groups( as in the aspect to be discussed hereinafter) are involved.

We have found that by employing a substance of the type described above curls are produced which have less tendency to relax upon drying of the hair and actually contract to some degree. We believe that on alkylation the broken idisulfide bonds are joined to the open chain compound aforesaid by true covalent linkages substantially in accordance with the structural equation set forth below.

As already mentioned, covalent bonds tighten on drying as true atomic distances are assumed, and we believe this accounts for the contraction on drying of curls present in hair hardened by alkylation pursuant hereto. Moreover, We believe that the general tightness of the curl after drying is directly related to the fact that there is only'a single carbon atom between the sulfur atoms joined during hardening in accordance with our system. We believe further that inclusion of more than one carbon atom between the sulfur atoms results in looser curl formation caused by greater atomic distances between the rejoined sulfur atoms, and we have found that when such greater distances are present the resulting curls are inferior to those obtainable with conventional oxidation methods of hardening.

Important factors in the selection of an appropriate compound of the type specified above are non-corrosiveness, non-staining, blandness, relative non-toxicity, relat-ive non-irritability, relative non-malodorousness or obnoxiousness, and commercial availability.

A substance meeting all of the foregoing requirements is 2,2,2 trichloro, 1,1, ethanediol. To produce an acceptable wave, a hardening solution comprising 2,2,2 trichloro, 1,1, ethanediol should contain at least 2.5% by weight of 2,2,2 trichloro, 1,1, ethanediol. We have found that not more than 2 by weight is necessary. Enough reharding to restore the hair to its original resilient condition occurs even at the minimum percentage, but with increasing percentage, the time required for rehardening decreases. Thus, it takes approximately ten minutes to reharden su-fliciently to restore the hair with a solution containing the minimum amount of 2,2,2, trichloro, 1, 1,

ethanediol and approximately five minutes when the maximum amount is present. A concentration of higher than 20% Will work satisfactorily but without appreciable decrease in time, so that employing more than 20% is both unnecessary and wasteful. The optimal percentage based 4 on commercial considerations such as speed and price is from 5 to 10% by weight.

The pH range for carrying out hardening pursuant to the instant aspect of the present invention is 1 to 7, with the optimum curl being obtained at pHs of 1 to 3. The following are examples of materials satisfactory for adjusting pH to the optimum level: Citric acid, tartaric acid, succinic acid, pyruvic acid, acetic acid, hydrochloric acid and lactic acid.

A complete hair waving process embodying the aspect of the present invention now under discussion is set forth below.

( 1) The hair is blocked off.

(2) The hair is wetted with a mercaptan waving solution containing 6.6% by weight of thioglycollic acid and having a pH of 9.4.

The hair is wound up in curlers.

The hair is rewetted with the waving solution.

The hair is allowed to process for five to fifteen minutes.

The hair is rinsed with lukewarm water.

A hardening agent in accordance with the present invention is applied to the hair.

The hair is allowed to stand for five to ten minutes. The hair is taken out of the curlers.

The hair is rinsed.

A typical formulation embodying the instant invention as applied to permanent waving follows:

2,2,2 trichloro, 1,1, ethanediol IOgms. Citric acid 0.15 gm. to produce a pH of 2.6. Sodium-N-Methyl-N-oleoyl taurate (wetting agent) 0.10 gm.

Water, q.s. to ccs.

The waving'process is carried out as previously set forth above.

Typical other wetting agents employable with compositions embodying the aspect of the invention above are:

(l) Alkyl phenoxy polyoxethylene ethanol (2) Polyoxyethylene sorbitan monolaurate (3) Hydrolysed gelatin condensate of oleic acid chloride In addition, clouding agents, perfumes, colors, conditioning agents, emollients or thickeners may be used in minor amounts in the hardening solution to enhance the usefulness and efficacy of the solution.

Pursuant also to the aspect of the present invention described above, hardening may be carried out in accordance therewith in the presence of conventional oxidizing agents. This may be desirable if less contraction of the curls after drying is desired; also, from the point of view of. price, it may be preferable to employ oxidizing agents in conjunction with a hardening agent embodying the instant invention in order to reduce the overall cost, less of the alkylating agent being required where oxidizing agents are present. The more oxidizing agent employed, the less of the alkylating agent that will be required.

With the standard i.e. conventional percentage of oxidizing agent, to wit, 1.75 grams of hydrogen peroxide in .100 ccs. of water, 0.10% by weight 2,2,2-trichloro-1,1-

2,2,2-trichloro-1,l-ethanediol 0.5 gm.

Hydrogen peroxide 1.75 gm.

Citric acid 0.15 gm. to pro- Sodium-n-methyl-m-oleoyl taurate duce a pH of 2.6.

(wetting agent) 0.1 gm.

Water, q.s. to 100 ccs.

snoaws The 2,2,2-trichloro-l,l-ethanediol is added to the peroxide solution either as crystals or in solution just prior to the hardening step. The waving process is carried out as set forth previously above.

Referring now to the setting aspect of the instant invention, we have found that a vow desirable and durable set can be simply and conveniently imparted to hair on the human head by use of an alkylating agent of the type described above in the proper manner and formulation. It is known that unreduoed keratin of hair on the human head has a number of naturally occurring free sul-fhydryl groups. We have found that when unsoftened hair, i.e. hair which has not immediately previously been reduced for permanent waving purposes, is subjected to treatment by an alkylating agent of the type described and is placed in waved configuration, the hair, upon drying, will have a temporary set which is highly resistant to dampness and physical displacement and will last longer than is the case with conventionaly applied sets.

We believe that the alkylating agent reacts with the free sulfhydryl groups of the unsoftened hair keratin and forms true covalent bonds between these groups whereby the chemical makeup of the hair is somewhat altered. For the reasons set forth previously in connection with the permanent waving aspect of the invention, a tightening of the curl or wave occurs on drying of the hair after treatment with the setting agent. And although the tightening effect is less than is the case Where immediately previously softened hair is rehardened by alkylation pursuant to the previously discussed aspect of the invention, the result is nevertheless a strengthening of the temporary set, with the desirable results mentioned above.

The various requirements set forth above for an alkylating agent to be used in hardening hair which is being permanently waved apply substantially as far as temporary setting is concerned, and again 2,2,2-trichloro-1,l-ethanediol meets these requirements. We have found that to produce an acceptable set the alkylating solution should contain at least 2% by Weight 2,2,2-trichloro-l,l-ethanediol. More than 20% by Weight is not needed. The setting solution should have a pH of about 5 to 7. In the inst-ant aspect of the invention, the optimum concentration of 2,2,2-trichloro-1,l-ethanediol is about and about 5.5 is the optimum pH. The pH of the solution is adjusted by means of the acids set forth previously herein.

The following is an example of a setting solution em'- bodying the instant aspect of the invention:

Gms. 2,2,2-trichloro-1,l-ethanediol 10.00 Natrosol (hydroxy ethyl cellulose-non ionic wetting agent) .25 Renex 3S (hydroxy alkyl etherwetting agent)" .2 Water, q.s. to 100 ccs.

The pH of this solution is 5.4.

The setting solution may be conveniently applied by a squeeze bottle directly to the hair after it has been thoroughly shampooed. The hair can be either completely dry or may be still wet after shampooing and prior to application of the setting solution. The latter is combed throughout the hair to distribute it evenly, and the hair is then curled with pin curis, rollers, or any other suit-able device for creating a waved configuration or curl. Thereafter, the hair is dried, and next it is removed from the curlers or the like. The hair may be placed in waved configuration before application or" the alkylatin-g agent.

The setting method and composition just described may be used conveniently in the home or in the beauty parlor. The tightening effect on drying, caused, We believe, by contraction of the hair as a result of alkylating of the free sulhydryl groups, imparts a long-lasting effect to the waved or curled configuration of the hair in the dry state.

Any relaxation caused by dampness or physical displacement is overcome to some extent on drying because of the contraction caused by alkylation; in other words, the hair is able to recover somewhat when the set is disturbed in a usual way short of shampooing. In addition, so long as some unreacted alkylating agent remains on the hair, the hair can be Wetted and newly set without further application of the alkylating agent. This is, of course, less effective than applying the agent anew, but it avoids continual applications of the agent between shampoos when the hair is accidentally Wet or when it is desired to change the set. The ability to accomplish this is of importance since the less chemical agent which is applied to the hair between shampoos the better for its appearance.

It thus will be seen that there are provided compositions of matter and methods for permanently iwaving and temporarily setting hair on the human head which achieve the several objects of the invention and are well adapted to meet the conditions of practical use.

As various possible embodiments might be made of the above invention and as various changes might be made in the embodiments above set forth, it is to be understood that all matter hereinabove described is to be interpreted as illustrative and not in a limiting sense.

Having thus dscribed our invention, we claim as new and desire to secure by Letters Patent:

1. In a method of treating hair on the human head to affect the configuration thereof, the step of joining the sulfur atoms of sulfhydryl groups of keratin present in said hair by alkylation through the application to the hair of an aqueous solution containing at least 2% by weight 2,2,2-ltnichloro, l l ethanediol.

2. in a method of setting hair on the human head which has not been immediately previously thereto softened for permanent waving: the step of joining naturally occurring free sulfhydryl groups of the keratin in the hair by applying to the hair an aqueous solution containing at least 2% by weight 2,2,2 trichloro,1,1 ethanediol, said solution having a. pH of 5 to 7.

3. In a method of permanently waving hair on the human head wherein the hair is softened by reducing and placed in waved configuration: the step of then hardening the hair by applying thereto an aqueous solution containing at least 2.5% by weight 2,2,2 trichloro,1,l, etha ediol said solution having a pH of 1 to 7.

4. In a method of permanently waving hair on the hu man head wherein the hair is softened by reducing and placed in waved configuration: the step of then hardening the hair by applying thereto an aqueous solution containing 5 to-'10% by weight 2,2,2 trichloro,1,1, ethanediol, said solution having a pH of 1 to 3.

5. In a method of permanently waving hair on the human head wherein the hair is softened by reducing and placed in waved configuration: the step of then hardening the hair by applying thereto an aqueous solution of 2,2,2 trichloro,1,1, ethanediol, said solution also containing an oxidizing agent selected from the group consisting oi hydrogen peroxide and alkaline perborates and bromates.

6. A solution for use as a hardening agent for hair on the human head that has been softened by reducing, said solution comprising water, 2,2,2 trichloro, 1,1, eth anediol and an oxidizing agent selected from the group consisting of hydrogen peroxide and alkaline perborates and bromates.

References {Zited in the file of this patent UNITED STATES PATENTS 2,403,906 Burke July 16, 1946 2,434,562 Harris Ian. 13, 1948 2,739,033 Lubs Mar. 20, 1956 

6. A SOLUTION FOR USE AS A HARDENING AGENT FOR HAIR ON THE HUMAN HEAD THAT HAS BEEN SOFTENED BY REDUCING, SAID SOLUTION COMPRISING WATER, 2,2,2 TRICHLORO, 1,1 ETHANEDIOL AND AN OXIDIZING AGENT SELECTED FROM THE GROUP CONSISTING OF HYDROGEN PEROXIDE AND ALKALINE PERBORATES AND BROMATES. 